EP0084772B1 - Pfropfmodifizierte Siloxandispersionen zur Ausrüstung von textilen Materialien - Google Patents

Pfropfmodifizierte Siloxandispersionen zur Ausrüstung von textilen Materialien Download PDF

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Publication number
EP0084772B1
EP0084772B1 EP83100041A EP83100041A EP0084772B1 EP 0084772 B1 EP0084772 B1 EP 0084772B1 EP 83100041 A EP83100041 A EP 83100041A EP 83100041 A EP83100041 A EP 83100041A EP 0084772 B1 EP0084772 B1 EP 0084772B1
Authority
EP
European Patent Office
Prior art keywords
weight
vinyl
textile
graft
organopolysiloxane
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired
Application number
EP83100041A
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German (de)
English (en)
French (fr)
Other versions
EP0084772A3 (en
EP0084772A2 (de
Inventor
Heinrich Dr. Alberts
Helmut Dr. Steinberger
Wilfried Dipl.-Ing. Kortmann
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Bayer AG
Original Assignee
Bayer AG
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Filing date
Publication date
Application filed by Bayer AG filed Critical Bayer AG
Priority to AT83100041T priority Critical patent/ATE24217T1/de
Publication of EP0084772A2 publication Critical patent/EP0084772A2/de
Publication of EP0084772A3 publication Critical patent/EP0084772A3/de
Application granted granted Critical
Publication of EP0084772B1 publication Critical patent/EP0084772B1/de
Expired legal-status Critical Current

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Classifications

    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
    • D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M15/643—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds containing silicon in the main chain
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
    • D06M15/21—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M15/356—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of other unsaturated compounds containing nitrogen, sulfur, silicon or phosphorus atoms
    • D06M15/3568—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of other unsaturated compounds containing nitrogen, sulfur, silicon or phosphorus atoms containing silicon

Definitions

  • the present invention relates to textile finishing agents which contain siloxane graft copolymers.
  • Silicones are used in the textile industry as water repellents. Compared to other strongly hydrophobic substances, e.g. As paraffin and waxes, silicones have the advantage that they have no fat character, which has a favorable effect on the "handle" of the treated fabric, that they can be fixed on the fiber in such a way that they can be washed or solvent treated to a comparatively high degree Withstand textiles, that they are largely resistant to chemicals and weather and that they ultimately have a remarkable softening and smoothing effect on the textile, but the softening effect of the silicones has such an effect on some textiles (cotton, polyester, polyamide) that treated textile finally attacks softly and lobularly, which can be undesirable for some applications.
  • some textiles cotton, polyester, polyamide
  • acrylates or polyacrylates and methacrylates can be used to increase the stiffness of fabrics.
  • these products do not give the textiles the desired elasticity and resilience, even when used in combination with silicones.
  • the object of the invention is achieved in that special graft copolymers are used to finish textile material.
  • graft modification of organopolysiloxanes with vinyl monomers is described, for example, in GB-A-766528, GB-A-806 582, GB-A-869 482 and DE-B-1 694 973. It is also known from US-A-4166 078 to modify Si-H-siloxanes by grafting with vinyl monomers. Furthermore, US-A-4172101 describes the graft modification of vinyl-substituted polysiloxanes.
  • the mixtures of polymethylhydrogensiloxanes, vinyl group-containing polysiloxanes and vinyl monomers are subjected to radical polymerization with the addition of radical formers and, if appropriate, molecular weight regulators.
  • Stable dispersions are obtained which consist of an organopolysiloxane component and polymerized units of one or more vinyl monomers and which contain graft polymers of organopolysiloxanes which are cross-bridged via polymerized units of the vinyl monomers used, part of the Si-H groups of the polymethylhydrogensiloxanes being modified by monoaddition of the vinyl compounds used.
  • graft polymers produced in this way are soluble or dispersible in water; Even with a high silicone content, these polymers can be easily emulsified in water with relatively little emulsifier additives.
  • the radical polymerization of the vinyl monomers can be started in a manner known per se with the aid of radical formers, UV rays, a, ⁇ or y rays or thermally without further additives.
  • the radiation-initiated polymerization is preferably carried out in the presence of sensitizers, cf. e.g. A.D. Jenkins, A. Ledwith, Reactivity, Mechanism and Structure in Polymer Chemistry, John Wiley + Son, London, New York, 1974, p. 465.
  • radical formers are used in amounts between 0.001 to 2, preferably 0.02 to 0.8% by weight, based on the total mixture of organopolysiloxane, radical formers and vinyl monomers.
  • Azo initiators such as azobis-isobutyronitrile (AIBN), azo esters, azo imino esters or azo-N-alkyl amides, peroxides such as di-tert-butyl peroxide, di-cumyl peroxide, di-benzoyl peroxide, peresters such as amyl perpivalate, tert .-Butyl perpivalate, tert-butyl peroctoate, tert-butyl perbenzoate, tert-butyl perneodecanoate, percarbonates such as cyclohexyl percarbonate or bisisopropyl percarbonate or hydroperoxides such as Cumyl hydroperoxide,
  • AIBN azobis-isobutyroni
  • Suitable initiators are also benzpinacol, benzpinacol derivatives or other thermally labile, highly substituted ethane derivatives.
  • the polymerization can also be started with the help of redox systems at temperatures lower than the purely thermal decomposition temperatures of the radical formers.
  • peroxides and amines such as e.g. Benzoyl peroxide and triethylamine, trialkylboron compounds and oxygen, hydroperoxides and sulfinic acids, formaldehyde or aldoses or combinations with low-quality transition metal salts and sulfur dioxide / peroxide redox systems.
  • the polymerization reaction can be carried out continuously or batchwise, without pressure or at reaction pressures up to, for. B. 300 bar, preferably up to 15 bar, at reaction temperatures between -20 ° C and + 250 ° C, preferably 70 to 190 ° C.
  • the polymerization can also be carried out in the presence of solvents or diluents, water, alcohols such as methanol, ethanol, tert-butanol, aliphatic or aromatic hydrocarbons, halogenated hydrocarbons such as chlorobenzene or fluorinated compounds, ethers such as dioxane or tetrahydrofuran, Esters such as Ethyl acetate.
  • solvents or diluents water, alcohols such as methanol, ethanol, tert-butanol, aliphatic or aromatic hydrocarbons, halogenated hydrocarbons such as chlorobenzene or fluorinated compounds, ethers such as dioxane or tetrahydr
  • the polymerization reaction can be carried out in the presence of molecular weight regulators.
  • molecular weight regulators such as Mercaptans such as n- or tert-dodecyl mercaptan, thioglycol, thioglycerol or thioacetic acid esters may be mentioned as regulators.
  • sulfur-free molecular weight regulators such as hydrocarbons, examples include paraffin fractions such as. As petroleum ether, light or white spirit, a-olefins such.
  • B. propylene, isobutylene, butene-1, furthermore ketones such. As acetone, methyl ethyl ketone or cyclohexanone, also aldehydes such as. B.
  • allyl ethers which are derived on the one hand from aliphatic or cycloaliphatic aldehydes or ketones and on the other hand from alkyl, cycloalkyl or aralkyl alcohols are suitable for the process.
  • the cycloaliphatic aldehydes or ketones can be substituted or bridged in the ring and / or contain a double bond.
  • Examples include butyraldehyde, valeraldehyde, cyclohexylaldehyde, cyclohexenylaldehyde, bicyclo [2,2,1] hexenylaldehyde and cyclohexanone.
  • Preferred are the cycloaliphatic aldehydes or ketones, which are optionally substituted by one or two C, -C, alkyl groups, in particular by methyl groups in the ring.
  • Suitable alcohols are C 1 -C 20 alkanols, which optionally may be branched or unsaturated and C 5 -C 10 cycloalkanols and Cy-C zo -Aralkylalkohole whose cycloalkyl or aryl group may be optionally substituted by lower alkyl radicals.
  • Examples include methanol, ethanol, n-propanol, isobutanol, 2-ethylhexanol, cyclohexanol and benzyl alcohol.
  • the enol ethers used as molecular weight regulators are used in amounts of 0.01-10% by weight, preferably 0.05-1% by weight, based on the sum of the monomers.
  • the enol ethers can be added at any time during the polymerization, preferably the enol ether used as regulator is added at the beginning of the polymerization.
  • Also suitable as telogens are halogenated hydrocarbons such as methylene chloride, tetrachloroethane, dibromoethane, etc. As expected, the viscosities of the dispersions can be controlled with the aid of such regulators.
  • the graft polymers can be prepared by bringing mixtures of a terminally vinyl-functional organopolysiloxane, a methylhydrogenpolysiloxane and one or more vinyl monomers in the presence of a radical generator to a reaction temperature which triggers the polymerization. If desired, mixtures of terminally vinyl-functional and non-functional organopolysiloxanes can also be introduced into the reaction mixture.
  • the polymerization can be carried out by a continuous or batch process. In principle, the order of addition of the components to be reacted is arbitrary, but the best results are achieved if mixtures of vinylsiloxane and hydrogen siloxane and vinyl monomers are used simultaneously in the course of the polymerization reaction.
  • the conversion of the monomers used is determined by the chosen polymerization process and the reaction conditions. In the batchwise polymerization mode, the highest possible conversions are aimed at, so that at least 80% of the monomers used, but preferably more than 90%, are converted.
  • the residual monomers are removed by known methods by distillation at normal pressure or under reduced pressure. The residual monomer contents which were effectively found in the dispersions after working up are negligibly low, they are generally below 1,000 ppm, preferably below 100 ppm.
  • This monoaddition changes the polarity and hydrophobicity of the polysiloxane chain and improves the interaction with the textile substrate.
  • the silicone-vinyl polymer! Sates according to the invention are particularly suitable for the coating and finishing of natural or synthetic fibers, threads or textile fabrics. They give textile articles both the voluminous soft feel that is characteristic of silicone, as well as permanent elasticity and resilience.
  • the silicone-vinyl polymers according to the invention have an emulsifying behavior which is comparatively more favorable than that of pure silicones of corresponding viscosity.
  • the emulsifiers used expediently consist of a mixture of a hydrophilic and a hydrophobic component.
  • Suitable compounds are, for example, fatty acid esters of polyhydric alcohols, such as stearic acid esters of glycols, glycerol or sorbitol, as well as higher fatty alcohols or the adducts of ethylene oxide with these fatty alcohols, fatty acids or similar compounds with an active hydrogen atom.
  • anion-active emulsifiers such as sodium lauryl sulfate or sodium dodecylbenzenesulfonate or cation-active emulsifiers such as quaternary ammonium compounds are also suitable.
  • silicone-vinyl copolymers according to the invention are applied to the substrate to be treated by the known methods, for example by padding, drying and condensing, by spraying or slapping.
  • the silicone graft polymer component can be thermally or catalytically crosslinked, if appropriate with the addition of further reactive silicone derivatives such as e.g. Polymethylhydrogensiloxanen done.
  • the purely thermal crosslinking takes place at temperatures from around 120 ° C.
  • the catalytically activated crosslinking can take place at room temperature.
  • Known systems such as platinum or platinum compounds, organotin compounds but also peroxides or other radical initiators are suitable as catalysts.
  • UV-activated crosslinking can also be carried out successfully. Crosslinking improves the solvent and wash resistance of the equipment. In the case of catalytic crosslinking, it is advisable to use appropriate inhibitors, such as Use acetylene alcohols, especially methylenedinol.
  • the polydiorganosiloxanes are prepared in a manner known per se (cf. W. Noll, “Chemistry and Technology of Silicones”, Verlag Chemie, Weinheim / Bergstrasse, 2nd ed., 1968, chap. 5, p. 162 ff.).
  • siloxanes listed in the examples are identified as follows:
  • the mixture is stirred for 1 hour and then the volatile constituents are removed by distillation.
  • the mixture is stirred at 150 ° C. for 1 hour, then evacuated and virtually completely freed of unreacted monomers.
  • the graft polymer obtained has a viscosity of 1500 mPas at 25 ° C. and has a composition which corresponds to an 88% monomer conversion.
  • the application takes place in the manner described above.
  • DMDHEU dimethyldihydroxyethylene urea
  • acrylate dispersions and plasticizers based on fatty acid amides and / or silicones are added to the finishing liquor.
  • the application is carried out by diving (picking up liquor 70-100% of the weight of the goods), squeezing and then drying. This is followed by a calendering and condensation step at 140-160 ° C for 4 to 6 minutes.
  • Example 11 In comparison to Example 11, the advantageous handle, tear resistance and crease angle remain practically unchanged in Example 15 according to the invention even after 5 washes at 60 ° C., while Example 11 after 5 washes under the same conditions shows significant deteriorations in the handle (rough, empty) and significant reduction of tear resistance and crease angle.
  • a 100% co-circular knitted fabric (100 kg) structured in the longitudinal direction is dyed with reactive dyes on a nozzle dyeing machine, rinsed hot and cold several times and soaped at cooking temperature; so that all unfixed dye components are removed.
  • the last rinsing bath remains in the machine.
  • 2 kg of the graft copolymer according to the invention from Example 4 (corresponds to 2% of the total weight) are passed through a batch vessel.
  • the pH of the rinsing liquor was previously adjusted to 6.0 with acetic acid.
  • the treatment bath is at 1 ° C / min. heated to 35 ° C. After reaching the final temperature, the goods remain for 15 minutes. in the equipment fleet.
  • the liquor is then drained off, the goods are removed from the dyeing apparatus and dried continuously at 125 ° C.
  • the handle of the treated goods is full, soft and smooth.
  • the test serves to determine the elongation and the resilience (resilience) of textile fabrics under certain static tensile loads with subsequent relief.
  • 3 strip-shaped samples 300 mm long and 50 mm wide are taken from the textile fabrics to be tested in the warp and weft directions, and in knitted fabrics in the longitudinal and transverse directions.
  • the samples are clamped in an upper fixed and a lower movable clamping clamp so that 50 mm protrude from the upper and lower clamp.
  • the middle 100 mm are identified as the measuring section.
  • a weight is attached to the lower clamp, which together with the weight of the clamp results in a test force of 25 N (2.5 Kp).
  • the elongation of the test specimen is measured and the static elongation in% is calculated from the change in length.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Graft Or Block Polymers (AREA)
  • Silicon Polymers (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
  • Silicon Compounds (AREA)
  • Pens And Brushes (AREA)
  • Curing Cements, Concrete, And Artificial Stone (AREA)
EP83100041A 1982-01-16 1983-01-05 Pfropfmodifizierte Siloxandispersionen zur Ausrüstung von textilen Materialien Expired EP0084772B1 (de)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AT83100041T ATE24217T1 (de) 1982-01-16 1983-01-05 Pfropfmodifizierte siloxandispersionen zur ausruestung von textilen materialien.

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE19823201205 DE3201205A1 (de) 1982-01-16 1982-01-16 Pfropfmodifizierte siloxandispersionen zur ausruestung von textilen materialien
DE3201205 1982-01-16

Publications (3)

Publication Number Publication Date
EP0084772A2 EP0084772A2 (de) 1983-08-03
EP0084772A3 EP0084772A3 (en) 1983-08-24
EP0084772B1 true EP0084772B1 (de) 1986-12-10

Family

ID=6153211

Family Applications (1)

Application Number Title Priority Date Filing Date
EP83100041A Expired EP0084772B1 (de) 1982-01-16 1983-01-05 Pfropfmodifizierte Siloxandispersionen zur Ausrüstung von textilen Materialien

Country Status (8)

Country Link
US (1) US4464506A (pt)
EP (1) EP0084772B1 (pt)
JP (1) JPS58126378A (pt)
AT (1) ATE24217T1 (pt)
BR (1) BR8300181A (pt)
DE (2) DE3201205A1 (pt)
ES (1) ES8402895A1 (pt)
FI (1) FI75878C (pt)

Families Citing this family (21)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4684670A (en) * 1983-08-26 1987-08-04 General Electric Company Ultraviolet radiation-curable silicone release compositions
JPH01168971A (ja) * 1987-12-23 1989-07-04 Nisshin Kagaku Kogyo Kk 繊維用弾性加工剤及び風合改良剤
JPH01168972A (ja) * 1987-12-25 1989-07-04 Nisshin Kagaku Kogyo Kk 親水性を付与する繊維用弾性加工剤
JP2703603B2 (ja) * 1989-02-09 1998-01-26 日信化学工業株式会社 繊維用処理剤
JP3007121B2 (ja) * 1990-08-02 2000-02-07 東レ・ダウコーニング・シリコーン株式会社 オルガノポリシロキサン―アクリル酸エステル系共重合体エマルジョン
JP2513101B2 (ja) * 1992-01-23 1996-07-03 信越化学工業株式会社 エアバッグ用コ―ティング組成物及びエアバッグ
JP2960304B2 (ja) * 1993-06-30 1999-10-06 信越化学工業株式会社 繊維用撥水処理剤
US5413724A (en) * 1993-12-30 1995-05-09 Dow Corning Corporation Fiber treatment compositions and methods for the preparation thereof
US5464801A (en) * 1993-12-30 1995-11-07 Dow Corning Corporation Catalyst compositions comprising rhodium catalyst complexes
DE59600007D1 (de) * 1995-03-09 1997-08-07 Wacker Chemie Gmbh Bindemittel für textile Flächengebilde
DE19629585C2 (de) * 1995-09-06 1998-12-10 Heidenhain Gmbh Dr Johannes Winkelmeßeinrichtung
US6375685B2 (en) * 1997-05-13 2002-04-23 The Procter & Gamble Company Textile finishing process
EP1026202B1 (en) * 1997-10-24 2004-04-07 Daikin Industries, Ltd. Aqueous resin dispersion composition
EP1520927B1 (en) 1998-09-30 2007-08-01 Unilever Plc Treatment for fabrics
ATE277158T1 (de) * 2000-12-15 2004-10-15 Unilever Nv Textilwaschmittel
US6616980B2 (en) 2001-04-24 2003-09-09 Crompton Corporation Emulsion polymerized acrylated silicone copolymer for wrinkle reduction
US20070100072A1 (en) * 2003-07-25 2007-05-03 Hiroshi Akitomo Silicone rubber composition
US7452957B2 (en) * 2005-08-31 2008-11-18 Kimberly-Clark Worldwide, Inc. Hydrophilic silicone elastomers
EP2091982B1 (en) * 2006-12-12 2013-04-24 Unilever PLC Improvements relating to branched organic-inorganic polymers
JP7008432B2 (ja) * 2017-03-31 2022-01-25 信越化学工業株式会社 シリコーンが固着された繊維及びその製造方法
WO2018180615A1 (ja) 2017-03-31 2018-10-04 信越化学工業株式会社 電子線固着用繊維処理剤

Family Cites Families (11)

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NL125765C (pt) * 1963-11-29
US3555109A (en) * 1967-09-08 1971-01-12 Stauffer Wacker Silicone Corp In situ generation of unique particulate matter in organopolysiloxanes
US3627836A (en) * 1968-11-15 1971-12-14 Stauffer Wacker Silicone Corp Modified organopolysiloxanes with mono and polyolefinic cross-linked particles generated in situ
BE754668A (fr) * 1969-08-13 1971-02-10 Stauffer Wacker Silicone Corp Organopolysiloxanes modifies et leur preparation
US4014851A (en) * 1973-12-26 1977-03-29 General Electric Company Polyolefin-filled vinyloranopolysiloxane composition and method of preparation
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DE2608894A1 (de) * 1976-03-04 1977-09-08 Pfersee Chem Fab Verfahren zur herstellung von modifizierten polymerisaten und deren verwendung
US4070526A (en) * 1976-05-20 1978-01-24 Dow Corning Corporation Radiation-curable coating compositions comprising mercaptoalkyl silicone and vinyl monomer, method of coating therewith and coated article
DE2641201A1 (de) * 1976-09-14 1978-03-16 Consortium Elektrochem Ind Diorganopolysiloxane enthaltende gemische und verfahren zu ihrer herstellung
US4166078A (en) * 1977-12-16 1979-08-28 Sws Silicones Corporation Modified organopolysiloxane compositions
US4172101A (en) * 1978-04-14 1979-10-23 Sws Silicones Corporation Modified organopolysiloxane compositions

Also Published As

Publication number Publication date
EP0084772A3 (en) 1983-08-24
FI75878C (fi) 1988-08-08
FI830122L (fi) 1983-07-17
US4464506A (en) 1984-08-07
DE3201205A1 (de) 1983-07-28
EP0084772A2 (de) 1983-08-03
ES519008A0 (es) 1984-02-16
BR8300181A (pt) 1983-10-11
FI830122A0 (fi) 1983-01-13
ES8402895A1 (es) 1984-02-16
DE3368302D1 (en) 1987-01-22
ATE24217T1 (de) 1986-12-15
FI75878B (fi) 1988-04-29
JPS58126378A (ja) 1983-07-27

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